U.S. patent number 4,212,771 [Application Number 05/931,330] was granted by the patent office on 1980-07-15 for method of preparing an alumina catalyst support and catalyst comprising the support.
This patent grant is currently assigned to Exxon Research & Engineering Co.. Invention is credited to Glen P. Hamner.
United States Patent |
4,212,771 |
Hamner |
July 15, 1980 |
Method of preparing an alumina catalyst support and catalyst
comprising the support
Abstract
A catalyst support is prepared by grinding a calcined alumina to
a powder, compacting the powder at an elevated pressure, recracking
the compressed powder to a predetermined size particle and acid
extracting the particle. The support can be composited with
catalytic components such as hydrogenation components and/or
zeolites and used in a variety of hydrocarbon treating processes,
such as hydrorefining, hydrodesulfurization, hydroconversion,
reforming, and catalytic cracking.
Inventors: |
Hamner; Glen P. (Baton Rouge,
LA) |
Assignee: |
Exxon Research & Engineering
Co. (Florham Park, NJ)
|
Family
ID: |
25460612 |
Appl.
No.: |
05/931,330 |
Filed: |
August 8, 1978 |
Current U.S.
Class: |
502/64; 502/254;
502/258; 502/324; 502/332 |
Current CPC
Class: |
B01J
21/04 (20130101); B01J 37/0036 (20130101); B01J
37/06 (20130101); C10G 49/02 (20130101) |
Current International
Class: |
B01J
21/04 (20060101); B01J 21/00 (20060101); B01J
37/00 (20060101); B01J 37/06 (20060101); C10G
49/00 (20060101); C10G 49/02 (20060101); B01J
029/06 (); B01J 029/04 (); B01J 023/08 () |
Field of
Search: |
;252/455R,455Z,463 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Dees; Carl F.
Attorney, Agent or Firm: Gibbons; Marthe L.
Claims
What is claimed is:
1. A process for the preparation of a catalyst support which
comprises the steps of:
(a) grinding a calcined alumina to a powder having a diameter
ranging from about 10 to about 400 mesh Tyler, and
(b) extracting the ground alumina with an extractant comprising an
acid selected from the group consisting of inorganic acids and
organic acids, for a time sufficient to remove at least 1 weight
percent of said alumina from said ground alumina.
2. The process of claim 1 wherein said powder resulting from step
(a) is compacted at an elevated pressure to form a compacted
aggregate and wherein said compacted aggregate is formed into a
predetermined size particle and, thereafter, extracting said
predetermined size particle with said extractant.
3. The process of claim 1 wherein said calcined alumina is ground
to a powder having a diameter ranging from about 10 to about 100
mesh Tyler.
4. The process of claim 2 wherein said powder is compacted at a
pressure of at least 20,000 psig.
5. The process of claim 1 or claim 2 wherein said acid is an
inorganic acid.
6. The process of claim 2 wherein after said extraction step, the
acid extracted predetermined size particle is dried.
7. The process of claim 2 wherein said particle formed from said
compacted aggregate has a size ranging from about 1/8 to about 1/64
inch in diameter.
8. The process of claim 2 wherein said particle formed from said
compacted aggregate has a size ranging from about 10 to about 400
mesh Tyler.
9. The process of claim 2 wherein said particle formed from said
compacted aggregate has a size ranging from about 10 to about 100
mesh Tyler.
10. The process of claim 6 wherein said extractant also comprises
an alcohol that may easily be removed during said drying stage.
11. The process of claim 1 or claim 2 wherein said calcined alumina
of step (a) additionally comprises a minor amount of at least one
oxide of a Group IIA, Group IIIA, Group IVA and Group IVB of the
Periodic Table of Elements.
12. The process of claim 1 or claim 2 wherein said calcined alumina
of step (a) additionally comprises a minor amount of silica.
13. The process of claim 6 wherein said dried particle is calcined
at a temperature ranging from about 750.degree. to about
1200.degree. F.
14. A process for the preparation of a catalyst support which
comprises the steps of:
(a) grinding a calcined alumina to a powder having a diameter
ranging from about 10 to about 400 mesh Tyler;
(b) compacting said powder at an elevated pressure to produce a
compacted aggregate;
(c) forming said compacted aggregate into a predetermined size
particle;
(d) extracting the predetermined size particle with an extractant
comprising an acid selected from the group consisting of inorganic
acids and organic acids, at a temperature ranging from about 60 to
about 150.degree. F. for a time sufficient to remove from about 2
to about 10 percent alumina from said predetermined size
particle;
(e) drying said acid extracted predetermined size particle; and
(f) calcining said dried particle.
15. A process for the preparation of a catalyst which comprises the
steps of:
compositing at least one catalytic component selected from the
group consisting of (i) a crystalline aluminosilicate zeolite, (ii)
a metal component selected from the group consisting of a metal or
a compound of a metal from the group of IB, IIA, IIIB, IVA, IVB,
VB, VIB, VIIB, VIII, rare earth metals and mixtures thereof, with
an alumina support prepared by the steps which comprise: (a)
grinding a calcined alumina to a powder, and (b) extracting the
ground alumina with an extractant comprising an acid selected from
the group consisting of inorganic acids and organic acids, for a
time sufficient to remove at least one weight percent of said
alumina from said ground alumina.
16. The process of claim 15 wherein said powder resulting from step
(a) is compacted at an elevated pressure to form a compacted
aggregate and wherein said compacted aggregate is formed into a
predetermined size particle and, subsequently, extracting said
predetermined size particle with said extractant.
17. The process of claim 15 or claim 16 wherein the acid extracted
alumina, without intervening calcination, is composited with said
metal component and wherein the resulting composite is
calcined.
18. The process of claim 15 or claim 16 wherein said catalytic
component comprises a crystalline aluminosilicate zeolite.
19. The process of claim 15 or claim 16 wherein said catalytic
component comprises a metal component selected from the group
consisting of Group VIB and Group VIII of the Periodic Table of
Elements.
20. The process of claim 15 or claim 16 wherein said metal
component is selected from the group consisting of IB, IVA, VIA,
VIB, VIII and mixtures thereof of the Periodic Table of
Elements.
21. The process of claim 15 or claim 16 wherein after said
extraction step, the remaining acid extracted alumina is dried and
subsequently calcined.
22. The process of claim 21 wherein said catalyst comprises a metal
component selected from the group consisting of a metal or compound
of a metal of Group IVB and Group VIII and mixtures thereof and
wherein after said drying step, the resulting dried particles are
composited with said metal component.
23. The process of claim 15 wherein said calcined alumina is ground
to a powder having a diameter ranging from about 10 to about 100
mesh Tyler.
24. The process of claim 16 wherein said calcined alumina is ground
to a powder having a diameter ranging from about 10 to about 400
mesh Tyler.
25. The process of claim 16 wherein said powder is compacted at a
pressure of at least about 20,000 psig.
26. The process of claim 15 or claim 16 wherein said acid is an
inorganic acid.
27. The process of claim 21 wherein said extractant comprises an
alcohol that may easily be removed during said drying step.
28. The process of claim 16 wherein said particle formed from said
compacted aggregate has a size ranging from about 1/8 to about 1/64
inch in diameter.
29. The process of claim 16 wherein said particle formed from said
compacted aggregate has a size ranging from about 10 to about 400
mesh Tyler.
30. The process of claim 16 wherein said particle formed from said
compacted aggregate has a size ranging from about 10 to about 100
mesh Tyler.
31. The process of claim 15 or claim 16 wherein said calcined
alumina of step (a) additionally comprises a minor amount of at
least one oxide of a Group IIA, Group IIIA, Group IVA and Group IVB
of the Periodic Table of Elements.
32. The process of claim 15 or claim 16 wherein said calcined
alumina of step (a) additionally comprises a minor amount of
silica.
33. The process of claim 15 or claim 16 wherein said catalyst
comprises a metal component and wherein said catalyst has a surface
area ranging from about 200 to about 400 m.sup.2 /g, a pore volume
ranging from about 0.5 to about 1.0 cc/g; and an average pore
diameter ranging from about 80 to about 200 Angstroms.
34. The process of claim 1 wherein said extractant also comprises a
C.sub.1 to C.sub.4 aliphatic alcohol.
35. The process of claim 15 wherein said extractant also comprises
a C.sub.1 to C.sub.4 aliphatic alcohol.
36. The process of claim 15, wherein said metal component is
selected from the group consisting of cobalt, cobalt oxide, cobalt
sulfide, nickel, nickel oxide, nickel sulfide, molybdenum,
molybdenum sulfide, molybdenum oxide, tungsten, tungsten oxide,
tungsten sulfide and mixtures thereof.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for the preparation of an
alumina catalyst support, a catalyst comprising the support and
hydrocarbon treating processes utilizing the catalyst.
2. Description of the Prior Art
It is known to extract calcined alumina which may have been formed
into the desired shape with an acid to dissolve a portion of the
alumina and, thereby, produce an alumina catalyst support
substantially free of pores smaller than 70 Angstroms while having
a pore volume substantially the same as that of the non-acid
extracted alumina. See U.S. Pat. No. 3,038,865.
It is known to prepare active alumina agglomerates of high
mechanical strength by treating pellets of alumina in an autoclave
in an acidic medium at a temperature above 100.degree. C. for 1 to
20 hours, followed by drying the treated pellets and calcining the
dried pellets. See U.S. Pat. No. 3,628,914.
A process for the manufacture of a pellet type of catalyst is known
which comprises wet grinding a metal oxide, such as alumina, to
obtain particles having a size less than 40 microns, and
thereafter, molding the mass of particles into pellets at elevated
pressures. See U.S. Pat. No. 2,921,033.
It is also known to increase the macroporosity of calcined alumina
by treating the calcined alumina with certain organic acids, such
as dicarboxylic acids. See U.S. Pat. No. 3,997,476.
A catalyst is also known having a total pore volume comprised of
micropores and access channels, the latter being interstitially
spaced throughout the structure of the micropores. The access
channels having diameters between 100 and 1000 Angstroms constitute
10 to 40 percent of the total pore volume and the access channels
having diameters greater than 1000 Angstroms constitute 10 to 40
percent of the pore volume while the remainder of the pore volume
comprises 20 to 80 percent of micropores with diameters less than
100 Angstroms. See U.S. Pat. No. 3,630,888.
Hydroconversion in the presence of an ebullated catalytic
macroporous microspheres smaller than 60 mesh and larger than 325
mesh (U.S. Standard), is known. See U.S. Pat. No. 3,622,500.
Pressures ranging from 5 to 20 tons per square inch to pelletize a
mixture of catalyst constituents are known. Calcination can be
conducted before or after pelleting. See U.S. Pat. No.
3,846,286.
It has now been found that a catalyst support prepared in
accordance with the present invention will provide advantages that
will become apparent in the ensuing description
By the term "hydrotreating" is intended herein the contacting of a
hydrocarbon feed with a catalyst in the presence of hydrogen under
selected conditions to remove heteroatoms such as sulfur, oxygen
and metallic contaminants such as nickel, vanadium and iron from
the feedstock and/or to saturate aromatic hydrocarbons and/or
olefinic hydrocarbons in the feedstock and/or to hydrocrack the
feedstock.
The term "hydroconversion" is used herein to designate a catalytic
hydrotreating process conducted in the presence of hydrogen in
which at least a portion of the heavy constituents of the
hydrocarbonaceous feedstock is converted to lower boiling
hydrocarbon products. Simultaneously, the concentration of
nitrogenous compounds, sulfur compounds and metallic contaminants
of the feedstock may be reduced.
SUMMARY OF THE INVENTION
In accordance with the invention there is provided, a process for
the preparation of a catalyst support which comprises the steps of:
(a) grinding a calcined alumina to a powder, and (b) extracting the
ground alumina with an extractant comprising an acid for a time
sufficient to remove at least one weight percent of the alumina
from the ground alumina.
When a support of a size greater than powder size is desired, the
powder is compacted at elevated pressure to produce a compacted
aggregate which is subsequently formed into a predetermined size
particle. The acid extraction stage is then performed on the
predetermined size particle.
The support may be composited with conventional catalytic
components such as zeolites, hydrogenation components, reforming
components and the like to produce catalysts which can be utilized
in catalytic hydrocarbon treating processes.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plot showing nickel removal versus time during
hydroprocessing of a Jobo crude utilizing a catalyst of the present
invention.
FIG. 2 is a plot showing vanadium removal versus time during
hydroprocessing of a Jobo crude utilizing a catalyst of the present
invention.
FIG. 3 is a plot showing sulfur removal versus time during
hydroprocessing of a Jobo crude utilizing a catalyst of the present
invention.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst support of the present invention is produced by a
sequence of steps which comprises grinding a calcined alumina to a
powder. Suitable calcined aluminas for use as starting material are
any of the conventionally available aluminas. Preferably, the
calcined alumina is an eta or gamma alumina. The average pore size
diameter of the initial calcined alumina may range from about 50 to
about 250 Angstroms. The pore size diameter for pores above 200
Angstroms referred to herein is determined using a Mercury
penetration porosimeter model 915-2 manufactured by Micromeritics
Corporation, Norcross, Georgia. The surface tension of the mercury
is taken at 474 dynes per centimeter at 25.degree. C. and a contact
angle of 140 degrees. The calculation of pore volume distribution
is similar to that used by Orr Powder Technology, Volume 3,
1960-1970, pages 117-123. For example, a suitable calcined alumina
is a gamma alumina having an average pore size diameter ranging
from 50 to 200 Angstroms and a pore volume ranging from 0.3 to
1.5.
The calcined alumina may additionally comprise a minor amount of an
oxide of at least one metal of Groups IIA, IIIA, IVA, IVB and
mixtures thereof of the Periodic Table of Elements such as silica,
zirconia, magnesia, thoria, etc. The Periodic Table referred to
herein is in accordance with the table published by E. H. Sargent
and Company, copyright 1962, Dyna Slide Co. When the calcined
alumina comprises an additional oxide, the alumina is present in
major amount, that is, it comprises more than 50 weight percent of
the calcined composite, preferably more than 98 weight percent of
the calcined composite used as starting material. A preferred
calcined alumina for use as starting material is gamma alumina
composited with from about 1 to about 6 weight percent silica, such
as the catalyst support disclosed in Adams et al. U.S. Pat. No.
3,509,044. The calcined alumina starting material, which may
additionally comprise a minor amount of the above-mentioned oxides,
is ground to a powder having a particle size ranging from about 10
to about 400 mesh Tyler. The resulting powder is compacted at an
elevated pressure, preferably at a pressure of at least 20,000
psig, more preferably at a pressure of at least 40,000 psig to
produce a compacted aggregate. The compacted aggregate is formed
into a particle of a predetermined size, for example, by breaking
the aggregate to obtain the desired size particles, suitably
particles of 14 to 35 mesh Tyler which are equivalent to 1/32 inch
extrudates. When the support is intended for a catalyst to be used
in a fixed bed process, the particles are made into 1/8 to 1/64,
typically 1/32 inch particles. When the support is intended for a
catalyst to be used in a slurry process, particles having a size
ranging from about 10 to about 400 mesh Tyler (20 to 150 microns),
typically 100 mesh Tyler, are produced. When the ultimately desired
size particle is the size obtained from the grinding step, for
example, a powder having particles ranging from about 10 to about
100 mesh Tyler, then the steps of compacting the powder to form an
aggregate and acid extracting can be omitted. After the compacted
powder has been formed into the predetermined size particle, the
predetermined size particle is extracted with an extractant which
comprises an acid. The extractant may additionally comprise an
alcohol. The extraction is performed by contacting the
predetermined size alumina-containing particle with the extractant
for a time sufficient to remove at least 1 weight percent,
preferably from about 2 to about 10 weight percent alumina from the
alumina present in the predetermined size particle. It is believed
that the extraction step removes preferentially the alumina which
is present in the interstitial spaces and that, therefore, the
extraction step clears the interstitial spaces, thereby permitting
easier access of the feed molecules into the pores of the support.
Suitable acids for use in the extractant are inorganic acids and
organic acids. Preferably, an inorganic acid is used such as
HNO.sub.3, etc. Suitable concentrations of acids include from about
1 to 20 weight percent, preferably from about 2 to about 15 weight
percent, more preferably from about 5 to about 10 weight percent
acid based on the alumina being treated. Suitable alcohols that may
be included in the extractant solution comprise methyl, ethyl,
isopropyl or higher boiling alcohols that may easily be removed
during the drying stage.
The acid extraction is conducted at a temperature ranging from
about 60.degree. F. to about 150.degree. F., preferably at a
temperature ranging from about 70 to about 100.degree. F., and
atmospheric pressure for a period of time sufficient to remove the
desired amount of alumina from the particle. Suitable time periods
include from about 1 to about 24 hours, preferably from about 2 to
about 16 hours. The temperature, pressure and time of treatment are
not critical provided the desired amount of alumina is removed from
the ground alumina without otherwise adversely affecting the ground
alumina.
After the alumina-containing particle of predetermined size has
been acid treated, it is separated from the extractant, for
example, by filtration or decantation, washed, dried in air or in a
vacuum oven and subsequently calcined, for example, at a
temperature ranging from about 750 to about 1200.degree. F.,
preferably at a temperature ranging from about 950 to about
1000.degree. F. for a period of time ranging from about 1 to about
16 hours.
To produce a catalyst, known catalytic components are composited
with the support. The catalytic components which may be zeolites,
metals, metal compounds or mixtures thereof may be composited with
the support at any appropriate stage. When the catalytic component
is a metal or metal compound, it is preferably added to the support
after the drying step and prior to the calcination step, that is,
the composite of alumina support plus catalytic metal component is
calcined without an intervening calcination of the support itself.
If desired, the finished catalyst may be sulfided prior to use in a
conventional manner.
The alumina-containing ground and acid extracted support may be
advantageously used as support for catalytic components which
function as hydrocarbon treating catalysts. Thus, the support can
be composited with one or more of the known metal components which
catalyze hydrocarbon reactions. In general, these metals or
compound of such metals include Groups IB, IIA, IIIB, IVA, IVB, VB,
VIB, VIIB, VIII and rare earth lanthanide series. For use in
hydrotreating processes including hydrorefining,
hydrodesulfurization, hydrodenitrogenation, hydrodemetallization,
hydroconversion and hydrocracking, the support of the present
invention is composited by conventional techniques with metals and
metal compounds of Groups VIB and VIII. For hydrorefining,
hydrodemetallization, hydrodesulfurization and hydroconversion, the
support of the present invention is composited with metals and
metal compounds of Group IVB and non-noble metals and metal
compounds of Group VIII, such as, for example, molybdenum,
tungsten, nickel and cobalt components either alone or in
combination thereof. For use in hydrotreating, preferably the
catalytic metal component is a hydrotreating component selected
from the group consisting of cobalt, cobalt oxide, cobalt sulfide,
nickel, nickel oxide, nickel sulfide, molybdenum, molybdenum
sulfide, molybdenum oxide, tungsten, tungsten oxide, tungsten
sulfide and mixtures thereof. Suitable amounts of hydrotreating
metal components in the finished catalyst comprising the support of
the present invention are from about 8 to about 30 percent,
preferably from about 12 to about 20 percent Group VIB metal
component calculated as the metal oxide and from about 1 to about 6
weight percent, preferably from about 3.5 to about 5.0 weight
percent Group VIII metal component, calculated as the metal oxide,
based on the total finished catalyst. For reforming low octane
naphtha to a higher octane product, the support of the present
invention is composited by conventional techniques with a noble
metal and other metal modifiers of Groups VIII, VIB, IVB, IB, IVA,
VIA, such as platinum, iridium, rhenium, palladium, copper,
chromium, zirconium, tin and selenium. Suitable concentrations
include from about 0.05 to about 5, preferably from about 0.1 to
1.0 weight percent noble metal of Group VIII and from about 0.02 to
about 2 weight percent metal modifiers. The ground and acid
extracted alumina support may additionally comprise from about 0.1
to about 2 weight percent of a Group IIA, Group IIIB, Group IV
component or mixtures thereof, such as magnesium, calcium,
lanthanum and calcium.
For use in catalytic cracking processes in the absence of added
hydrogen, the ground and acid extracted alumina may be composited
with conventional catalytic cracking components such as inorganic
oxide cracking components and/or zeolites. Suitable inorganic oxide
components for use with the ground and acid extracted alumina of
the present invention include silica, silica-alumina,
silica-zirconia, silica-magnesia, alumina-boria, alumina-titania
and the like and mixtures thereof. The crystalline aluminosilicate
zeolite may be chosen from any of the known zeolites. Examples of
these zeolites include the zeolites designated by the Linde
Division of Union Carbide by the letters X, Y, A, L (these zeolites
are described in U.S. Pat. Nos. 2,882,244; 3,130,007; 2,882,243 and
Belgian Pat. No. 575,117, respectively), ultrastable Y-type
zeolites described, for example, in U.S. Pat. Nos. 3,293,192 and
3,402,996 and the publication, Society of Chemical Engineering
(London) Monograph Molecular Sieves, p. 186 (1968) by C. V.
McDaniel and P. K. Maher; zeolite ZSM-5 described in U.S. Pat. No.
3,702,866 and in Nature, vol. 272, Mar. 30, 1978, pp. 437-438, as
well as naturally occurring zeolites such as faujasite, chabazite,
erionite, mordenite, offretite, gmelinite, analcite, etc. The
zeolites, as produced or found in nature normally contain an alkali
metal such as sodium and/or potassium and/or an alkaline earth
metal such as calcium and magnesium. The zeolites differ from each
other in structure, composition and particularly in the ratio of
silica to alumina contained in the crystal lattice structure. For
use in hydrocarbon conversion processes the higher ratio silica to
alumina among isostructural zeolites are preferred because of their
stability at elevated temperature, particularly in the presence of
steam. Therefore, whereas the zeolite component to be used in
combination with the ground and acid extracted alumina of the
present invention may be any of the above-stated zeolites, the
zeolites having silica to alumina ratios above 3 will be preferred.
This includes natural and synthetic faujasite and mordenite. The
crystalline zeolites have uniform pore openings ranging in diameter
from 3 to 15 Angstroms. The preferred pore size zeolite component
for use with the support of the present invention will be zeolites
having uniform pore size diameters ranging from about 6 to about 15
Angstroms. It is usually necessary to reduce the alkali metal
content of the zeolite to a content of less than 10 weight percent,
preferably less than 6 weight percent and more preferably about 1
to 5 weight percent since the alkali metal components are normally
undesirable catalytic components for the desired hydrocarbon
conversion reaction. The alkali metal content reduction may be
accomplished, as is well known in the art, by exchange with any one
or more of the cations selected from Group IB through Group VIII
metals of the Periodic Table of Elements, as well as hydrogen
cation or hydrogen precursor (i.e., NH.sub.4.sup.+) capable of
conversion to hydrogen cation. The preferred cations are those
selected from the Group consisting of rare earth metals, calcium,
magnesium, hydrogen and mixtures thereof. A particularly preferred
zeolite is "ultrastable" Y-type faujasite. In general,
"ultrastable" refers to a Y-type zeolite which is resistant to
degradation of crystallinity by high temperatures and steam
treatment and is characterized by an R.sub.2 O content (wherein R
is Na, K, or any other alkali metal ion) of less than 1 weight
percent and a unit cell size less than 24.50 A and a SiO.sub.2
/Al.sub.2 O.sub.3 mole ratio in the range of 3.5 to 7 or higher.
The ultrastable form of the Y-type zeolite is obtained by the
virtual elimination of the alkali metal ion and the unit cell size
reduction after the alkali metal removal step. The zeolite
component may suitably be present in an amount ranging from about 2
to about 20 weight percent of the final cracking catalyst. The
ground and acid extracted alumina of the present invention may
range from about 2 to about 40, preferably from about 2 to about 25
weight percent of the final cracking catalyst.
The physical characteristics of the final catalyst starting with a
calcined gamma alumina are given in Table I.
TABLE I ______________________________________ Typical Physical
Characteristics Broad Example
______________________________________ Surface Area, m.sup.2 /g
200-400 290 Pore Volume, cc/g 0.5-1 0.7 Averge Pore Diameter, A
80-200 120 Pore Volume Distribution, cc/g Less than 30 A 2-10 5
30-100 A 70-80 75 Above 500 A 5-30 20 Particle Size, Inches 1/8 to
1/32 for Fixed Bed 1/64 Particle Size, Mesh 10-400 100 for Slurry
Bed ______________________________________
A specific embodiment of a catalyst preparation method of the
present invention for a fixed bed catalyst is as follows:
Grinding a commercially available calcined alumina, such as gamma
alumina, to less than 100 mesh Tyler. Compressing the powder at
40,000 psig. Cracking the compressed powder to 14/35 mesh Tyler.
Extracting the 14/35 mesh particles with HNO.sub.3 (5-10% on
Al.sub.2 O.sub.3) in alcohol. Drying and impregnating with cobalt
and molybdenum salts. Air calcining at 950.degree. F. for 16 hours.
The catalyst of the present invention may be disposed in a fixed
bed including staged reactor systems, a moving bed, slurry,
fluidized bed, suspension, and ebullated bed.
The conditions and feeds suitable for hydrocarbon treating
processes in which the catalyst of the present invention can be
used are well known in the art.
Table II summarizes several typical reaction conditions effective
in the present invention.
TABLE II ______________________________________ Principal Reaction
Conditions Hydrogen Conversion Temperature Pressure, Feed Rate,
Rate, Desired .degree.F. psig V/V/Hr. SCF/bbl
______________________________________ Hydro- 500-800 50-5000
0.1-10.0 500-10,000 refining Hydro- 450-850 200-5000 0.1-2.0
500-20,000 cracking Catalytic 700-1000 0-50 0.1-20.0 -- Cracking
Catalytic 850-1000 50-1000 0.1-20 500-10,000 Reforming
______________________________________
Suitable hydrodesulfurization conditions are shown in Table
III.
TABLE III ______________________________________ Preferred
Preferred Conditions Broad Range Range.sup.(1) Range.sup.(2)
______________________________________ Temp., .degree.F. 400-850
450-700 650-825 Pressure, psig 100-5000 100-1500 1000-3000 Liquid
Hourly 0.05-3.0 0.5-5.0 0.1-0.5 Space Velocity V/V/Hr. Hydrogen
Rate, 300-20,000 200-4000 4000-16,000 SCF/bbl. Hydrogen Partial
100-5000 100-1200 1000-2500 Pressure, psig
______________________________________ .sup.(1) Naphthadistillate
feed .sup.(2) Residua feed
When it is desired to hydrodesulfurize the hydrocarbonaceous
feedstock with minimal hydrocarbon cracking, a substantially
non-acidic catalyst support is utilized.
Suitable hydroconversion conditions are shown in Table IV for
distillates and heavier feeds.
TABLE IV ______________________________________ Preferred
Conditions Broad Range Range ______________________________________
Temp., .degree.F. 500-850 650-750 Pressure, psig 800-5000 1500-3000
Liquid Hourly Space 0.1-5.0 0.25-2.0 Velocity V/Hr./V Hydrogen
Rate, 1000-20,000 2000-16,000 SCF/bbl Hydrogen Partial 800-5000
1000-2500 pressure, psig ______________________________________
The feedstocks suitable for the hydrocarbon treatment and
conversion of the present invention include any of the well known
feeds conventionally employed in hydrocarbon treating and
conversion processes.
Suitable hydrocarbonaceous feedstock for use in the
hydrodesulfurization process or in a hydroconversion process of the
present invention are heavy hydrocarbonaceous oils, particularly
sulfur-containing heavy hydrocarbonaceous oils such as whole
petroleum crude oils, including heavy crudes, topped or reduced
petroleum crude oils, heavy petroleum distillates such as gas oils;
petroleum atmospheric residuum; petroleum vacuum residuum; bitumen;
tar sand oil; shale oil; liquids derived from coal liquefaction
processes including coal liquefaction bottoms and mixtures thereof.
When the support of the present invention is composited with
hydrotreating catalytic components to produce a hydrotreating
catalyst, the resulting catalyst of the present invention is
particularly well suited for treating heavy crude oils and residual
oils that generally contain a high content of metallic contaminants
such as nickel, iron and vanadium and a high content of sulfur
compounds. The metal contents of such oils may range up to 2000
wppm or more and the sulfur content may range up to 8 weight
percent or more.
When the support of the present invention is the base for
conventional reforming catalytic components to produce reforming
catalysts, the feedstock would be a conventional feedstock (virgin,
hydrocrackate and catalytic naphthas) used in reforming processes,
for example, naphtha and conventional reforming conditions.
Similarly when the support of the present invention is composited
as a catalyst component with catalytic cracking components and used
in the absence of added hydrogen, conventional catalytic cracking
conditions and feedstocks may be used.
PREFERRED EMBODIMENTS
The following examples are presented to illustrate the
invention.
EXAMPLE 1
The calcined extrudates used as starting material to prepare a
catalyst of the present invention had the physical characteristics
shown in Table V.
TABLE V ______________________________________ ALUMINA INSPECTIONS
______________________________________ Surace area, m.sup.2 /g
(BET) 270 Pore volume, cc/g (BET) 0.54 Average Pore Diameter, A
(Calc.) 80 Macroporosity, cc/g.sup.(1) .05
______________________________________ .sup.(1) Mercury porosimeter
used to measure pores >500 A
A catalyst was prepared by extracting 100 grams of the calcined
alumina extrudates with a dilute nitric acid solution (5 wt. %
HNO.sub.3 acid on alumina dispersed in 500 ml. water) at room
temperature for 16 hours. The alumina was then filtered from the
acid solution, washed several times with water and then vacuum (26
inches Hg) air dried at 250.degree. F. to remove the absorbed
water. The acid extracted extrudates were then ground to 100-400
mesh material. The ground alumina was then compacted at 40,000 psig
to form a large solid mass of alumina; recracked to 14/35 mesh
material. The vacuum dried 14/35 mesh material obtained from the
re-constituted alumina was dispersed in 500 ml. of methyl alcohol
that contained 5 wt. % nitric acid based on alumina and then
treated at room temperature for 16 hours. The 14/35 mesh alumina
was removed by filtration from the alcohol-acid solution, alcohol
washed several times; vac-air dried at 250.degree. F. to remove the
excess alcohol from the pores of the acid extracted alumina and
finally impregnated with a methyl alcohol solution of cobalt
acetate and phosphomolybdic acid to result in a catalyst containing
3.5% cobalt and 16.6% molybdenum as the oxide on the acid extracted
alumina after drying and calcining at 950.degree. F. for 16 hours.
The finished catalyst, which is a catalyst of the present
invention, had the physical characteristics shown in Table VI.
TABLE VI ______________________________________ CATALYST
INSPECTIONS ______________________________________ Surface Area,
m.sup.2 /g 244 Pore Volume, cc/g .73 Macroporosity, cc/g.sup.(1)
0.31 Averge Pore Diameter, A (Calc.) 120
______________________________________ .sup.(1) Mercury porosimeter
used to measure pores >500A.
As can be seen from Tables V and VI, the catalyst of the invention,
when prepared on the acid extracted reconstituted ground alumina
had a six fold increase in macropore volume over that of the
original calcined alumina used as starting material.
EXAMPLE 2
Comparative hydrotreating experiments were made utilizing a Jobo
crude oil having the characteristics shown in Table VII.
TABLE VII ______________________________________ JOBO CRUDE
Inspections ______________________________________ Gravity,
.degree.API 8.9 Sulfur, Wt. % 4.29 Nitrogen, Wt. % 0.672 Metals,
ppm Ni 110 V 446 Carbon, Wt. % 84.69 Hydrogen, Wt. % 10.43
Conradson Carbon, Wt. % 16.7 %1050.degree. F.sup.+, Wt. % 55.7
______________________________________
The catalysts used in these experiments had equivalent chemical
compositions, but different physical properties. A commercially
available calcined gamma alumina having an average pore diameter of
about 80 Angstroms was used. All catalysts were impregnated to have
a metal level of 3.5 weight percent CoO and 16.6 weight percent
MoO.sub.3 on 14/35 mesh Tyler particles of alumina. Catalyst A was
prepared on the commercial alumina. The alumina was initially
extracted with a dilute water solution of nitric acid (5 weight
percent nitric acid to alumina) at room temperature for 16 hours in
order to extract a portion of the alumina. The acid extracted
alumina was then used as the catalyst support for Catalyst B and a
portion was ground to a fine powder. The ground alumina powder
portion was compacted at 40,000 psig, to form a large solid mass of
alumina, recracked to 14/35 mesh Tyler and a portion of the 14/35
mesh alumina was used as catalyst support for Catalyst C. The
remainder of the reconstituted 14/35 mesh alumina was then
extracted a second time with a like quantity of nitric acid in
methyl alcohol. The acid extracted 14/35 mesh alumina freed of
methanol was dried and used as the support for Catalyst D which is
a catalyst of the present invention. When using a water solution
for the second extraction step, the reconstituted 14/35 mesh
particles did not maintain their particle size, but appeared to be
similar in size to the ground alumina prior to compacting at 40,000
psig, thus indicating that the excess alumina within the
interstitial pores of the compacted aggregate had been extracted
and the alumina portion that gave the binding force (trash alumina
extracted) of the 14/35 mesh aggregate was removed by the
extraction step. The compositions and physical properties of the
catalyst are summarized in Table VIII.
TABLE VIII
__________________________________________________________________________
CATALYST.sup.(1) IDENTIFICATION AND INSPECTIONS Macro Porosity Data
B.E.T. Data P.V. in P.V. in P.V. in P.V. in Catalyst Treat S.A.
P.V. P.D. 500 A 5000 A 10,000 A 20,000A
__________________________________________________________________________
A Base Alumina, None 255 0.53 83 .029 .010 .009 .008 B HNO.sub.3
Extracted 277 0.59 85 .031 .010 .008 .008 C Powdered-Repilled 260
0.41 63 .021 .008 .006 .005 Al.sub.2 O.sub.3 Base for Catalyst B D
HNO.sub.3 Extracted 244 0.42 69 .113 .081 .067 .052 Al.sub.2
O.sub.3 Base for Catalyst C 0.71* 120*
__________________________________________________________________________
.sup.(1) Catalyst contains 3.5% CoO/16.6% MoO.sub.3. *Hg
porosimeter measurement indicating pore volume increase due to
interstitial pores created by the acid extraction and thus
calculated average pore diameter of 120 A. that is a blend of the
micro and macro pores.
Catalyst D is a catalyst in accordance with the present invention.
The remaining catalysts are reference catalysts.
The experiments were conducted at a pressure of 2200 psig with a
hydrogen rate of 4,000 SCF H.sub.2 /bbl at a space velocity of 1
V/V/Hr. The results of these experiments relative to nickel removal
are summarized in FIG. 1. The results of these experiments relative
to vanadium removal are summarized in FIG. 2. The results of these
experiments relative to sulfur removal are summarized in FIG.
3.
As can be seen from the data of these experiments, Catalyst D,
which is a catalyst in accordance with the present invention,
showed better vanadium and nickel removal from the feed than the
reference catalysts and maintained its activity at a lower level
for sulfur removal than the reference catalysts, even though twice
as much feed metal had been deposited for the time period being
evaluated. Catalyst C, lowest in macroporosity, deactivated the
fastest with Catalysts A and B also showing rapid decline for both
sulfur and metals after 300 hours of operation.
EXAMPLE 3
A ground commercial calcined alumina (100 grams) in powder form
(100-200 mesh) was dispersed in a solution of 500 ml. methyl
alcohol-5 grams of nitric acid for 16 hours at room temperature.
The acid extracted alumina was filtered from the solution, methyl
alcohol washed and then vac.-air dried at 250.degree. F. to remove
excess methyl alcohol. The acid extracted alumina was then
impregnated with a methyl alcohol solution of cobalt acetate and
phosphomolybdic acid to result in Catalyst E containing 3.5% cobalt
and 16.6% molybdenum as the oxide after drying and calcining at
950.degree. F. for 16 hours. The finished catalyst had the
following physical properties shown in Table IX and is a catalyst
in accordance with the present invention.
TABLE IX ______________________________________ CATALYST E
INSPECTIONS ______________________________________ Surface Area,
m.sup.2 /g 240 Pore Volume, cc/g 0.72 Macroporosity, cc/g.sup.(1)
0.22 Average Pore Diameter, A (Calc.) 120
______________________________________ .sup.(1) Mercury porosimeter
used to measure pores >500A
EXAMPLE 4
A portion of the ground commercial alumina (100-200 mesh) used for
the catalyst preparations in Example 3 was vac.-air dried and
impregnated with a methyl alcohol solution of cobalt acetate and
phosphomolybdic acid to result in Catalyst F containing 3.5% cobalt
and 16.6% molybdenum as the oxide after drying and calcining at
950.degree. F. for 16 hours. The finished catalyst had the physical
properties shown in Table X. Catalyst F is not a catalyst in
accordance with the present invention.
TABLE X ______________________________________ CATALYST F
INSPECTIONS ______________________________________ Surface Area,
m.sup.2 /g 245 Pore Volume, cc/g 0.53 Macroporosity, cc/g.sup.(1)
0.04 Average Pore Diameter, A (Calc.) 86
______________________________________ .sup.(1) Mercury porosimeter
used to measure pores >500A.
EXAMPLE 5
Comparative hydrotreating experiments with Catalysts E and F were
made utilizing a light Arabian atmospheric residuum feed having the
characteristics shown in Table XI.
TABLE XI ______________________________________ LIGHT ARABIAN
ATMOSPHERIC RESIDUUM ______________________________________
Gravity, .degree.API 15.3 Sulfur, Wt. % 3.46 Nitrogen, Wt. % 0.1708
Metals, ppm Ni 9.3 V 33.4 Carbon, Wt. % 85.47 Hydrogen, Wt. % 11.18
Conradson Carbon, Wt. % 9.83 % 1050.degree. F.sup.+, Wt. % 41.6
______________________________________
The experiments were conducted at a temperature of 700.degree. F.,
2200 psig, 0.25 V/V/Hr. with hydrogen gas rate of 16,000 SCF/bbl.
The results of the experiments are summarized below in Table
XII.
TABLE XII ______________________________________ HYDROPROCESSING
LIGHT ARABIAN ATMOSPHERIC RESIDUUM WITH 100-200 MESH CoMo Al.sub.2
O.sub.3 CATALYSTS Catalyst E Catalyst F (Acid (Non-Acid Extracted
Extracted Macro non Pore Macro Pore Catalyst) Catalyst)
______________________________________ Operating Conditions
Tempeature, .degree.F. 700 V/V/Hr. 0.25 Pressure, psig 2250 Gas
Rate, SCF/bbl. 16,000 Hours on Stream 200 Sulfur Activity, 1.5
Order 3.5 0.8 Liquid Product Inspections Gravity, .degree.API 28.0
23.0 Sulfur, Wt. % 0.021 0.22 Nitrogen, Wt. % 0.01 0.07 Conradson
Carbon, Wt. % 0.3 3.6 Metals, ppm Ni 0.04 0.5 V 0.01 0.2 % Sulfur
Removal 99.5 94.0 % Nitrogen Removal 95.0 54.9 % Conradson Carbon
Removal 96.9 64.7 % Metals Removal 100.0 99.0
______________________________________
The comparative data given in Table XII clearly shows improved
hydrotreatment of the atmospheric residuum feed when utilizing
Catalyst E that has been prepared according to the present
invention. The macropore catalyst shows essentially complete
removal of the heteroatom, Conradson carbon precursors and feed
metals or about ten fold lower sulfur and Conradson carbon content
and seven fold lower nitrogen content when compared with the
non-acid extracted low macropore Catalyst F. Even at this level of
conversion there was no apparent incompatible material present that
is normally associated with high conversions (85-90%) taught by the
art when processing residua feeds with less active, catalysts that
require high temperatures (>780.degree. F.) or hydro-thermal
conversion conditions.
* * * * *